2-aryl-2-(3-pyridyl)-1,3-dioxalanes, dithiolanes and -oxa-thiolanes having herbicidal and pesticidal activity

ABSTRACT

Fungicidal and herbicidal novel 3-substituted pyridines of the formula ##STR1## wherein A represents oxygen or sulfur, B represents oxygen, sulfur or sulfinyl, 
     R 1  represents hydrogen, halogen, alkyl or haloalkyl, 
     R 2  represents hydrogen, halogen, alkyl, phenyl, haloalkyl or phenoxy, 
     l is 0 or 1, 
     m is an integer from 1 to 4, 
     n is an integer from 1 to 5, and 
     w represents ##STR2##  in which R 3  and R 4  each represent hydrogen, hydroxyalkyl, alkoxyalkyl, alkyl, benzyloxyalkyl, haloalkyl or carboxyalkyl, or 
     R 3  and R 4  form a hydrocarbon ring having 3 to 12 carbon atoms in total together with the carbon atoms to which they are bonded, and 
     R 5 , R 6 , R 7  and R 8  each represent hydrogen, alkyl or hydroxyalkyl, provided that none of R 1 , R 2 , R 3 , and R 4  represents a hydrogen atom when A and B each represents oxygen, l is 0 and W represents ##STR3##

CROSS-REFERENCE

This is a continuation-in-part of application Ser. No. 268,913, filedNov. 8, 1988, now U.S. Pat. No. 4,940, 483.

The present invention relates to novel 3-substituted pyridines, toseveral processes for their preparation, and to their use asagricultural and horticultural fungicides and herbicides.

It has already been disclosed that2-phenyl-2-(pyridin-4-yl)-1,3-dioxolane was a reaction intermediate (seeHeterocycles, 22, 1137 (1984)), 2-phenyl-2-(pyridin-4-yl)-1,3-dithiolaneand 2-phenyl-2-(pyridin-4-yl)-1,3-dithiane were reaction intermediates[see J. Chem. Soc. Perkin Trans., I, 1223 (1984)] and2-phenyl-2-(pyridin-3-yl)-1,3-dioxolane was a reaction intermediate [seeBull. Soc. Chim. Belg., 89, 67 (1980)].

There have been found novel 3-substituted pyridines of the formula (I)##STR4## wherein A represents oxygen or sulfur, B represents oxygen,sulfur or sulfinyl,

R¹ represents hydrogen, halogen, alkyl or haloalkyl,

R² represents hydrogen, halogen, alkyl, phenyl, haloalkyl or phenoxy,

l is 0 or 1,

m is an integer from 1 to 4,

n is an integer from 1 to 5, and

W represents ##STR5## in which R³ and R⁴ each represents hydrogen,hydroxyalkyl, alkoxyalkyl, alkyl, benzyloxyalkyl, haloalkyl orcarboxyalkyl, or

R³ and R⁴ form a hydrocarbon ring having 3 to 12 carbon atoms in totaltogether with the carbon atoms to which they are bonded, and

R⁵, R⁶, R⁷ and R⁸ each represents hydrogen, alkyl or hydroxyalkyl,provided that none of R¹, R², R³ and

R⁴ represents a hydrogen atom when A and B both represent an oxygenatom, l is 0 and W represents ##STR6##

3-Substituted pyridines of the formula (I) are obtained when

(a) in the case where l is 0 and B represents oxygen or sulfur:

a compound of the formula (II): ##STR7## wherein R¹, R², m and n are asdefined above, is reacted with a compound of the formula (III):

    HA--W--B'H                                                 (III)

wherein A and W are as defined above, and

B' represents oxygen or sulfur,

in the presence of an inert solvent, and

in the presence of an acid catalyst,

or

(b) in the case where l is 1, and A and B each represents oxygen:

a compound of the formula (Ib) ##STR8## wherein R¹, R², m, n and W areas defined above, is reacted with an oxidizing agent,

in the presence of an inert solvent,

or

(c) in the case where B represents a sulfinyl group and l is 0 :

a compound of the formula (Ic) ##STR9## wherein R¹, R², m, n, A and Ware as defined above, is reacted with an oxidizing agent,

in the presence of an inert solvent.

The novel 3-substituted pyridines exhibit powerful fungicidal andherbicidal properties.

Surprizingly, the 3-substituted pyridines according to the inventionexhibit a substantially greater fungicidal and herbicidal action thanthose known from the prior art, for instance, abovementioned Bull. Soc.Chim. Belg., 89,67 (1980), J. Chem. Soc. Perkin Trans. I 1223 (1984) andHeterocycles 22 1137 (1984).

Among the 3-substituted pyridines according to the invention of theformula (I), preferred compounds are those wherein A and B eachrepresents oxygen or sulfur,

R¹ represents hydrogen or chlorine,

R² represents hydrogen, chlorine, bromine, fluorine, alkyl having 1 to 4carbon atoms, or phenyl,

m and n are each 1 or 2, and

W represents ##STR10## in which R³ and R⁴ each represents hydrogen,alkyl having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 3 carbonatoms, alkoxyalkyl having 2 to 4 carbon atoms in total, or haloalkylhaving 1 to 4 carbon atoms, or

R³ and R⁴ form a hydrocarbon ring having 6 to 12 carbon atoms in totaltogether with the carbon atoms to which they are bonded, and

R⁵, R⁶, R⁷ and R⁸ each represents hydrogen, alkyl having 1 to 4 carbonatoms or hydroxyalkyl having 1 to 4 carbon atoms, provided that none ofR¹, R², R³ and R⁴ represents hydrogen when A and B each representsoxygen and, l is 0 ##STR11##

Very particularly preferred 3-substituted pyridines of the formula (I)are those

wherein A and B each represents oxygen or sulfur,

R¹ represents hydrogen, or chlorine,

R² represents hydrogen, chlorine, bromine, fluorine or methyl, or phenyl

n and m are each 1 or 2, and

W represents ##STR12## in which R³ and R⁴ each represents hydrogen,alkyl having 1 to 4 carbon atoms, methoxymethyl or chloromethyl,

or R³ and R⁴ form a cyclohexane ring together with the carbon atoms towhich they are bonded, and

R⁵, R⁶, R⁷ and R⁸ each represents hydrogen or alkyl having 1 to 3 carbonatoms, provided that none of R¹, R²,

R³ and R⁴ represents a hydrogen atom when A and B each represent oxygen,l is 0 and W represents ##STR13##

Specifically, the following compounds may be mentioned:

2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane,

4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane.

2-(2,4-dichlorophenyl)-5,5-diethyl-2-(3-pyridyl)-1,3-dioxane,

2-(4-chlorophenyl)-5,5-dimethyl-2-(3-pyridyl)-1,3-dioxane,

2-(biphenyl-4-yl)-5,5-diethyl-2-(3-pyridyl)-1,3-dioxane and

2-(2,4-dichlorophenyl)-5-ethyl-5-propyl-2-(3-pyridyl)-1,3-dioxane.

When in the process (a), for example, 3-benzoylpyridine and1,2-propanediol are used as starting materials, the course of thereaction can be represented by the following equation: ##STR14##

When in the process (b), for example,4-tert.-butyl-2-phenyl-2-(pyridin-3-yl)-1,3-dioxolane andm-chloroperbenzoic acid are used as starting materials, the course ofthe reaction can be represented by the following equation: ##STR15##

When in the process c, for example,2-phenyl-2-(pyridin-3-yl)-1,3-dithiane and m-chloroperbenzoic acid areused as starting materials, the course of the reaction can berepresented by the following equation: ##STR16## In the process (a), thestarting compounds of the formulae (II) and (III) mean compounds basedon the above definition of R¹, R², m, n, A, B' and W, preferablycompounds based on the above preferred definitions.

The compounds of the formulae (II) and (III) are known.3-Benzoylpyridine can be cited as an example of the formula (II).

1,2-ethane dithiol and 1,2-propane dithiol can be cited as examples ofthe formula (III).

In the processes (b) and (c), the starting compounds of the formulae(Ib) and (Ic) mean compounds based on the above definition of R¹, R², m,n, A and W, perferably compounds based on the above preferreddefinitions.

The compounds of the formula (Ib) and (Ic) can be prepared according tothe above-mentioned process (a).4-tert.-butyl-2-(4-chlorophenyl)-2-(pyridin-3-yl)-1,3-dioxolane can becited as an example of the formula (Ib) and2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane and4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane can be cited asexamples of the formula (Ic).

In the processes (b) and (c), hydrogen peroxide and m-chloroperbenzoicacid can be cited as examples of an oxidizing agent.

In carrying out the process (a), it is possible to use any inert organicsolvents as the suitable diluents. Examples of the diluents arealiphatic, cycloaliphatic and aromatic hydrocarbons which may bechlorinated hexane, cyclohexane, petroleum ether, ligroin, benzene,toluene, xylene, methylene chloride, chloroform, carbon tetrachloride,ethylene chloride, chlorobenzene, and the like; ethers such as diethylether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propyleneoxide, dioxane, tetrahydrofuran and the like; ketones such as acetone,methyl ethyl ketone, methyliso-propyl ketone, methyliso-butyl ketone,and the like; nitriles such as acetonitrile, propionitrile andacrylonitrile; alcohols such as iso-propanol; esters such as, forexample, ethyl acetate, amyl acetate, and the like; acid amides such asdimethyl formamide and dimethyl acetoamide; and sulfones and sulfoxidessuch as dimethyl sulfoxide, sulfolane, and the like.

The process (a) may be carried out in the presence of acid catalysts andas such catalyst may be mentioned, for example, sulfuric acid,hydrochloric acid, acid ion exchanging resin, methane sulfonic acid,ammonium chloride, para-toluene sulfonic acid, trifluoroboron-ethercomplex, aluminum chloride, zinc chloride and paratoluene sulfonic acidpyridinium salt.

In the process (a), the reaction temperature can be varied within asubstantially wide range. For instance, the reaction may be effected ata temperature between about -10° C. and about 200° C., preferably at atemperature of from about 50° C. to about 150° C. It is preferred tocarry out the reaction under normal pressure, although the use of ahigher or lower pressure is also allowable.

In carrying out the reaction of the process (a), use is made, forexample, of the compounds of the formula (III) in the mol amount from 1to 10 times and an acid catalyst in the amount of from 0.1 to 3 times,respectively, the mol amount of the above-mentioned compounds of theformula (II) in the presence of an inert solvent such as, for example,toluene, to obtain the desired compound.

In carrying out the reaction of the above-mentioned processes (b) and(c), use is made, as oxidizing agent, of organic peroxides such asmeta-chloroperbenzoic acid and hydrogen peroxide.

In carrying out the above-mentioned processes (b) and (c) with the useof organic peroxide as oxidizing agent, use may be made, as properdiluents, of any kind of inert organic solvents.

When the oxidizing agent is organic peroxide, examples of the diluentsare aliphatic, cycloaliphatic and aromatic hydrocarbons which may bechlorinated such as hexane, cyclohexane, petroleum ether, ligroin,benzene, toluene, xylene, methylene chloride, chloroform, carbontetrachloride, ethylene chloride, chlorobenzene and the like; alcoholssuch as methanol, ethanol, iso-propanol, butanol and ethylene glycol;esters such as, for example, ethyl acetate, amyl acetate and the like;and acid amides such as dimethylformamide and dimethylacetamide.

In carrying out the above-mentioned processes (b) and (c) with the useof hydrogen peroxide as oxidizing agent, the diluents to be used thereinmay be, for example, water that may be basic, neutral or acid, alcoholssuch as, for example, methanol, ethanol, iso-propanol, butanol andethylene glycol; and carboxylic acids such as, for example, acetic acid.

In each of the processes (b) and (c), the reaction temperature can bevaried within a substantially wide range. When use is made, as oxidizingagent, of organic peroxide, the reaction, in general, may be effected ata temperature between about -10° C. and about 50° C., preferably at atemperature of from about 0° C. to about 30° C.

Further, when use is made, as oxidizing agent, of hydrogen peroxide, thereaction, in general, may be effected at a temperature between about-10° C. and about 100° C., preferably at a temperature of from about 0°C. to about 30° C. It is preferred to carry out the reaction undernormal pressure, although the use of a higher or lower pressure is alsoallowable.

In carrying out the reaction of the process (b), use is made, forexample, of meta-chloroperbenzoic acid in the mol amount from 1 to 2times the mol amount of the above-mentioned compounds of the formula(Ib) in the presence of an inert solvent such as, for example, methylenechloride to obtain the desired compound.

In carrying out the reaction of the above-mentioned process (c), use ismade of meta-chloroperbenzoic acid in the mol amount of from 1 to 1.2times the mol amount of the above-mentioned compounds of the formula(Ic) in the presence of inert organic solvents such as methylenechloride to obtain the desired compound.

The active compounds according to the invention exhibit a powerfulmicrobicidal action and can be employed in practice for combatingundesired microorganisms. The active compounds are suitable for use asplant protection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericidal agents are employed in plant protection for combatingPseudomonoadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weedkillers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

Some causative organisms of fungal and bacterial diseases included underthe abovementioned main headings, are mentioned below as non-limitingexamples:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporacubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea

(Conidial form: Drechslera, Synonym: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Synonym: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention can also be used asweedkillers, for example, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be emplyed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the slective combating of weeds in annual cultures.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances, coatingcompositions for use on seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans and fumigatingcoils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents, diluents or carriers, there are suitable in themain, aromatic hydrocarbons, such as xylene, toluene or alkylnapthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons,such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight ofactive compound, preferably from 0.5 to 90 per cent by weight.

The active compounds, as fungicides, according to the invention can bepresent in the formulations or in the various use forms as a mixturewith other known active compounds, such as fungicides, bactericides,insecticides, acaricides, nematicides, herbicides, bird repellents,growth factors, plant nutrients and agents for improving soil structure.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, emulsions, suspensions, powders, pastesand granules. They are used in the customary manner, for example bywatering, immersion, spraying, atomizing, misting, vaoprising,injecting, forming a slurry, brushing on, dusting; scattering, drydressing, moist dressing, wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrations,as fungicides in the use forms can be varied within a substantial range.They are, in general, from 1 to 0.0001% by weight, preferably from 0.5and 0.001%.

For the treatment of seed, amounts of active compound of 0.001 to 50 g,especially 0.01 to 10 g, are generally employed per kilogram of seed.

For the treatment of soil, active compound concentrations, at the pointof action, of 0.00001 to 0.1% by weight, especially of 0.0001 to 0.02%,are generally employed.

The active compounds, as herbicides according to the invention, as suchor in the form of their formulations, can also be used, for combatingweeds, as mixtures with known herbicides, finished formulations or tankmixes being possible.

The active compounds, as herbicides according to the invention can beapplied either before or after emergence of the plants.

They can also be incorporated into the soil before sowing. They areused, in particular, after emergence of the plants.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.1 and 10 kg of active compound perhectare of soil surface, preferably between 0.5 and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 ##STR17##

1.83 g of 3-benzoylpyridine, 1.44 g of 1,2-propanediol and 2.43 g ofp-toluenesulfonic acid monohydrate were dissolved in a mixture of 15 mlof toluene and 15 ml of n-butanol and the resulting mixture was heatedunder reflux while removing the water thus formed therefrom. After thecompletion of the reaction, the solvents were distilled off in vacuo.The residue was dissolved in dichloromethane, washed with an aqueoussolution of sodium hydroxide and then with water and then dried overanhydrous sodium sulfate. After filtering off the sodium sulfate, thesolvent was distilled off in vacuo to thereby give4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dioxolane m.p.: 40°-44° C.

EXAMPLE 2 ##STR18##

To 25 ml of a solution of 1.5 g of 3-benzoyl-6-chloropyridine and 3.2 gof 1,2-propanediol in toluene, 1.2 g of boron trifluoride etherate wasadded. The resulting mixture was heated under reflux for six hours whileremoving the water thus formed therefrom. Then the reaction mixture wascooled, poured into an aqueous solution of sodium hydroxide andextracted with ether. The organic phase was washed with water and driedover anhydrous sodium sulfate. After filtering off the sodium sulfateand distilling off the solvent in vacuo,2-(6-chloropyridin-3-yl)-4-methyl-2-phenyl-1,3-dioxolane was obtainedm.p.: 44°-51° C.

EXAMPLE 3 ##STR19##

To 10 ml of a solution of 1.1 g of2-(4-chlorophenyl)-2-(pyridin-3-yl)-1,3-dithiane in methylene chloride,1.3 g of m-chloroperbenzoic acid was added under ice-cooling. Theresulting mixture was stirred under ice-cooling for 30 minutes and thenat room temperature for one hour followed by heating under reflux. Afterthe completion of the reaction, the crystals thus precipitated werefiltered off to thereby give2-(4-chlorophenyl)-2-(pyridin-3-yl)-1,3-dithiane-1-oxide n_(D) ²⁰ :1.3305.

EXAMPLE 4 ##STR20##

2.4 g of 4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dioxolane was dissolvedin a small amount of ethanol and 1.7 g of methyl iodide was addedthereto. The resulting mixture was stirred at room temperature for fourhours. After distilling off the solvent, the crystals thus obtained werewashed with dry ethanol to thereby give4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dioxolane methiodide, m.p.:125°-132° C.

EXAMPLE 5 ##STR21##

To 10 ml of a solution of 0.63 g of4-tert-butyl-2-(4-chlorophenyl)-2-(pyridin-3-yl)-1,3-dioxolane inmethylene chloride, 0.22 g of m-chloroperbenzoic acid was added and theresulting mixture was stirred at room temprature. After the completionof the reaction, the reaction mixture was poured into an aqueoussolution of sodium hydroxide and extracted with methylene chloride. Theorganic phase was washed with water and dried over anhydrous sodiumsulfate. After filtering off the sodium sulfate and distilling off thesolvent in vacuo, 4-tert-butyl-2-(4-chlorophenyl)-2-(pyridineN-oxide-3-yl)-1,3-dioxolane was obtained.

Table 1 shows the compounds of the present invention which may beobtained by the same methods as the above examples.

                                      TABLE 1    __________________________________________________________________________     ##STR22##     No.Comp.         ##STR23##                    ##STR24##     A                                    B   W                    PropertiesPhysica                                                            l    __________________________________________________________________________         ##STR25##                    ##STR26##    S S   CH.sub.2 CH.sub.2    mp. 60-61    2         ##STR27##                    ##STR28##    S S                                        ##STR29##           n.sub.D.sup.20                                                            1.6439    3         ##STR30##                    ##STR31##    S S   CH.sub.2 CH.sub.2 CH.sub.2                                                            mp. 96-98    4         ##STR32##                    ##STR33##    S S   CH.sub.2 CH.sub.2 CH.sub.2                                                            n.sub.D.sup.20                                                            1.5820    5         ##STR34##                    ##STR35##    S                                    ##STR36##                                       CH.sub.2 CH.sub.2 CH.sub.2    6         ##STR37##                    ##STR38##    O O                                        ##STR39##           mp. 40-44    7         ##STR40##                    ##STR41##    O O                                        ##STR42##           mp. 125-132    8         ##STR43##                    ##STR44##    O O                                        ##STR45##           n.sub.D.sup.20                                                            1.5600    9         ##STR46##                    ##STR47##    O O                                        ##STR48##           n.sub.D.sup.20                                                            1.5675    10         ##STR49##                    ##STR50##    O O                                        ##STR51##           n.sub.D.sup.20                                                            1.5812    11         ##STR52##                    ##STR53##    O O                                        ##STR54##           n.sub.D.sup.20                                                            1.5680    12         ##STR55##                    ##STR56##    O O                                        ##STR57##           n.sub.D.sup.20                                                            1.5646    13         ##STR58##                    ##STR59##    O O                                        ##STR60##           mp. 44-51    14         ##STR61##                    ##STR62##    O O                                        ##STR63##           n.sub.D.sup.20                                                            1.5730    15         ##STR64##                    ##STR65##    O O                                        ##STR66##           n.sub.D.sup.20                                                            1.5718    16         ##STR67##                    ##STR68##    O O                                        ##STR69##           n.sub.D.sup.20                                                            1.5485    17         ##STR70##                    ##STR71##    O O                                        ##STR72##           n.sub.D.sup.20                                                            1.5290    18         ##STR73##                    ##STR74##    O O                                        ##STR75##           n.sub.D.sup.20                                                            1.5305    19         ##STR76##                    ##STR77##    O O                                        ##STR78##           mp. 42-47    20         ##STR79##                    ##STR80##    O O                                        ##STR81##           n.sub.D.sup.20                                                            1.545 Oily    21         ##STR82##                    ##STR83##    O O                                        ##STR84##           n.sub.D.sup.20                                                            1.5188    22         ##STR85##                    ##STR86##    O O                                        ##STR87##           n.sub.D.sup.20                                                            1.5705    23         ##STR88##                    ##STR89##    O O                                        ##STR90##           Oily    24         ##STR91##                    ##STR92##    O O                                        ##STR93##           n.sub.D.sup.20                                                            1.5757    25         ##STR94##                    ##STR95##    O O                                        ##STR96##           n.sub.D.sup.20                                                            1.5931    26         ##STR97##                    ##STR98##    O O                                        ##STR99##           n.sub.D.sup.20                                                            1.5820    27         ##STR100##                    ##STR101##   O O                                        ##STR102##          n.sub.D.sup.20                                                            1.5550    28         ##STR103##                    ##STR104##   O O                                        ##STR105##          n.sub.D.sup.20                                                            1.5784    29         ##STR106##                    ##STR107##   S                                    ##STR108##                                        ##STR109##    30         ##STR110##                    ##STR111##   O O                                        ##STR112##          n.sub.D.sup.20                                                            1.5578    31         ##STR113##                    ##STR114##   O O                                        ##STR115##          mp. 108-115    32         ##STR116##                    ##STR117##   O O                                        ##STR118##          mp. 111-119    33         ##STR119##                    ##STR120##   O O                                        ##STR121##          n.sub.D.sup.50                                                            1.525-1.530    34         ##STR122##                    ##STR123##   O O   CH.sub.2 CH.sub.2 CH.sub.2                                                            mp. 73-81    35         ##STR124##                    ##STR125##   O O                                        ##STR126##          mp. 67-73    36         ##STR127##                    ##STR128##   O O                                        ##STR129##          mp. 88-92    37         ##STR130##                    ##STR131##   O O                                        ##STR132##          n.sub.D.sup.50                                                            1.5350    38         ##STR133##                    ##STR134##   O O                                        ##STR135##          mp. 102-104    39         ##STR136##                    ##STR137##   O O                                        ##STR138##          n.sub.D.sup.20                                                            1.5403    40         ##STR139##                    ##STR140##   O O                                        ##STR141##          n.sub.D.sup.20                                                            1.5765    41         ##STR142##                    ##STR143##   O O                                        ##STR144##          n.sub.D.sup.20                                                            1.5563    42         ##STR145##                    ##STR146##   O O                                        ##STR147##          n.sub.D.sup.20                                                            1.5340    43         ##STR148##                    ##STR149##   S                                    ##STR150##                                        ##STR151##    44         ##STR152##                    ##STR153##   S                                    ##STR154##                                        ##STR155##    45         ##STR156##                    ##STR157##   O O                                        ##STR158##    46         ##STR159##                    ##STR160##   O O                                        ##STR161##    47         ##STR162##                    ##STR163##   O O                                        ##STR164##          n.sub.D.sup.20                                                            1.5455    48         ##STR165##                    ##STR166##   O O                                        ##STR167##          n.sub.D.sup.20                                                            1.5330    49         ##STR168##                    ##STR169##   O O                                        ##STR170##    50         ##STR171##                    ##STR172##   O O                                        ##STR173##    51         ##STR174##                    ##STR175##   O O                                        ##STR176##    52         ##STR177##                    ##STR178##   O O                                        ##STR179##          mp. 87-100    53         ##STR180##                    ##STR181##   O O                                        ##STR182##          n.sub.D.sup.20                                                            1.5592    54         ##STR183##                    ##STR184##   S                                    ##STR185##                                       CH.sub.2CH.sub.2CH.sub.2    55         ##STR186##                    ##STR187##   O O                                        ##STR188##          n.sub.D.sup.20                                                            1.5750    56         ##STR189##                    ##STR190##   O O                                        ##STR191##          n.sub.D.sup.20                                                            1.5519    57         ##STR192##                    ##STR193##   S S   CH.sub.2CH.sub.2     n.sub.D.sup.20                                                            1.6545    58         ##STR194##                    ##STR195##   S S                                        ##STR196##          n.sub.D.sup.22.5                                                            1.6394    59         ##STR197##                    ##STR198##   S S                                        ##STR199##          n.sub.D.sup.20                                                            1.6752    60         ##STR200##                    ##STR201##   S S                                        ##STR202##          n.sub.D.sup.20                                                            1.6286    61         ##STR203##                    ##STR204##   S                                    ##STR205##                                       CH.sub.2 CH.sub.2 CH.sub.2    62         ##STR206##                    ##STR207##   S S   CH.sub.2 CH.sub.2    63         ##STR208##                    ##STR209##   S S   CH.sub.2 CH.sub.2    64         ##STR210##                    ##STR211##   S S   CH.sub.2 CH.sub.2    65         ##STR212##                    ##STR213##   S                                    ##STR214##                                       CH.sub.2 CH.sub.2    66         ##STR215##                    ##STR216##   S                                    ##STR217##                                        ##STR218##    67         ##STR219##                    ##STR220##   S                                    ##STR221##                                       CH.sub.2CH.sub.2CH.sub.2                                                            n.sub.D.sup.20                                                            1.3305    68         ##STR222##                    ##STR223##   O O                                        ##STR224##    69         ##STR225##                    ##STR226##   O O                                        ##STR227##    70         ##STR228##                    ##STR229##   O O                                        ##STR230##    71         ##STR231##                    ##STR232##   S S                                        ##STR233##          n.sub.D.sup.20                                                            1.5828    72         ##STR234##                    ##STR235##   O O                                        ##STR236##          oily    73         ##STR237##                    ##STR238##   O O                                        ##STR239##          mp. 81-90°                                                            C.    74         ##STR240##                    ##STR241##   O O                                        ##STR242##          n.sub.D.sup.20                                                            1.5470    75         ##STR243##                    ##STR244##   O O                                        ##STR245##          n.sub.D.sup.20                                                            1.5720    76         ##STR246##                    ##STR247##   O O                                        ##STR248##          n.sub.D.sup.20                                                            1.5548    77         ##STR249##                    ##STR250##   O O   CH.sub.2 CH.sub.2    78         ##STR251##                    ##STR252##   O O   CH.sub.2 CH.sub.2    79         ##STR253##                    ##STR254##   O O   CH.sub.2 CH.sub.2    80         ##STR255##                    ##STR256##   O O                                        ##STR257##    81         ##STR258##                    ##STR259##   O O                                        ##STR260##    82         ##STR261##                    ##STR262##   O O                                        ##STR263##    83         ##STR264##                    ##STR265##   O O                                        ##STR266##    84         ##STR267##                    ##STR268##   O O                                        ##STR269##    85         ##STR270##                    ##STR271##   O O                                        ##STR272##    86         ##STR273##                    ##STR274##   O O                                        ##STR275##    87         ##STR276##                    ##STR277##   O O                                        ##STR278##    88         ##STR279##                    ##STR280##   O O                                        ##STR281##    89         ##STR282##                    ##STR283##   O O                                        ##STR284##    90         ##STR285##                    ##STR286##   O O                                        ##STR287##    91         ##STR288##                    ##STR289##   O O                                        ##STR290##    92         ##STR291##                    ##STR292##   O O                                        ##STR293##          oily    93         ##STR294##                    ##STR295##   O O                                        ##STR296##    94         ##STR297##                    ##STR298##   O O                                        ##STR299##    95         ##STR300##                    ##STR301##   O O                                        ##STR302##    96         ##STR303##                    ##STR304##   O O   CH.sub.2 CH.sub.2 CH.sub.2    97         ##STR305##                    ##STR306##   O O   CH.sub.2 CH.sub.2 CH.sub.2                                                            mp. 143-144.5.degr                                                            ee. C.    98         ##STR307##                    ##STR308##   O O                                        ##STR309##    99         ##STR310##                    ##STR311##   O O                                        ##STR312##    100         ##STR313##                    ##STR314##   O O                                        ##STR315##          mp. 111-115.degree                                                            . C.    101         ##STR316##                    ##STR317##   O O                                        ##STR318##    102         ##STR319##                    ##STR320##   O O                                        ##STR321##    103         ##STR322##                    ##STR323##   O O                                        ##STR324##    104         ##STR325##                    ##STR326##   O O                                        ##STR327##    105         ##STR328##                    ##STR329##   O O                                        ##STR330##    106         ##STR331##                    ##STR332##   O O                                        ##STR333##    107         ##STR334##                    ##STR335##   O O                                        ##STR336##    108         ##STR337##                    ##STR338##   O O                                        ##STR339##    109         ##STR340##                    ##STR341##   O O                                        ##STR342##    110         ##STR343##                    ##STR344##   O O                                        ##STR345##    111         ##STR346##                    ##STR347##   O O                                        ##STR348##    112         ##STR349##                    ##STR350##   O O                                        ##STR351##    113         ##STR352##                    ##STR353##   O O                                        ##STR354##    114         ##STR355##                    ##STR356##   O O                                        ##STR357##    115         ##STR358##                    ##STR359##   O O                                        ##STR360##    116         ##STR361##                    ##STR362##   O O                                        ##STR363##    117         ##STR364##                    ##STR365##   O O                                        ##STR366##    118         ##STR367##                    ##STR368##   O O                                        ##STR369##          mp. 132-140.degree                                                            . C.    119         ##STR370##                    ##STR371##   O O                                        ##STR372##    120         ##STR373##                    ##STR374##   O O                                        ##STR375##    121         ##STR376##                    ##STR377##   O O                                        ##STR378##    122         ##STR379##                    ##STR380##   O O                                        ##STR381##    123         ##STR382##                    ##STR383##   O O                                        ##STR384##    124         ##STR385##                    ##STR386##   O O                                        ##STR387##    125         ##STR388##                    ##STR389##   O O                                        ##STR390##    126         ##STR391##                    ##STR392##   O O                                        ##STR393##    127         ##STR394##                    ##STR395##   O O                                        ##STR396##    128         ##STR397##                    ##STR398##   O O                                        ##STR399##    129         ##STR400##                    ##STR401##   O O                                        ##STR402##    130         ##STR403##                    ##STR404##   O O                                        ##STR405##          oily    131         ##STR406##                    ##STR407##   O O                                        ##STR408##    132         ##STR409##                    ##STR410##   O O                                        ##STR411##    133         ##STR412##                    ##STR413##   O O                                        ##STR414##    134         ##STR415##                    ##STR416##   O O                                        ##STR417##    135         ##STR418##                    ##STR419##   O O                                        ##STR420##    136         ##STR421##                    ##STR422##   O O                                        ##STR423##    137         ##STR424##                    ##STR425##   O O                                        ##STR426##    138         ##STR427##                    ##STR428##   O O                                        ##STR429##    139         ##STR430##                    ##STR431##   O O                                        ##STR432##    140         ##STR433##                    ##STR434##   O O                                        ##STR435##    141         ##STR436##                    ##STR437##   O O                                        ##STR438##    142         ##STR439##                    ##STR440##   O O                                        ##STR441##    143         ##STR442##                    ##STR443##   O O                                        ##STR444##    144         ##STR445##                    ##STR446##   O O                                        ##STR447##    145         ##STR448##                    ##STR449##   O O                                        ##STR450##    146         ##STR451##                    ##STR452##   O O                                        ##STR453##    147         ##STR454##                    ##STR455##   O O                                        ##STR456##    148         ##STR457##                    ##STR458##   O O                                        ##STR459##    149         ##STR460##                    ##STR461##   O O                                        ##STR462##    150         ##STR463##                    ##STR464##   O O                                        ##STR465##    151         ##STR466##                    ##STR467##   O O                                        ##STR468##    152         ##STR469##                    ##STR470##   O O                                        ##STR471##    153         ##STR472##                    ##STR473##   O O                                        ##STR474##          n.sub.D.sup.20                                                            1.5852    154         ##STR475##                    ##STR476##   O O                                        ##STR477##    155         ##STR478##                    ##STR479##   O O                                        ##STR480##    156         ##STR481##                    ##STR482##   O O                                        ##STR483##    157         ##STR484##                    ##STR485##   O O                                        ##STR486##    158         ##STR487##                    ##STR488##   O O                                        ##STR489##    159         ##STR490##                    ##STR491##   O O                                        ##STR492##    160         ##STR493##                    ##STR494##   O O                                        ##STR495##    161         ##STR496##                    ##STR497##   O O                                        ##STR498##    162         ##STR499##                    ##STR500##   O O                                        ##STR501##    163         ##STR502##                    ##STR503##   O O                                        ##STR504##    164         ##STR505##                    ##STR506##   O O                                        ##STR507##    165         ##STR508##                    ##STR509##   O O                                        ##STR510##    166         ##STR511##                    ##STR512##   O O                                        ##STR513##          n.sub.D.sup.20                                                            1.5967    167         ##STR514##                    ##STR515##   O O                                        ##STR516##    168         ##STR517##                    ##STR518##   O O                                        ##STR519##    169         ##STR520##                    ##STR521##   O O                                        ##STR522##    170         ##STR523##                    ##STR524##   O O                                        ##STR525##    171         ##STR526##                    ##STR527##   O O                                        ##STR528##    172         ##STR529##                    ##STR530##   O O                                        ##STR531##    173         ##STR532##                    ##STR533##   O O                                        ##STR534##    174         ##STR535##                    ##STR536##   O O                                        ##STR537##    175         ##STR538##                    ##STR539##   O O                                        ##STR540##    176         ##STR541##                    ##STR542##   O O                                        ##STR543##    177         ##STR544##                    ##STR545##   O O                                        ##STR546##    178         ##STR547##                    ##STR548##   O O                                        ##STR549##    179         ##STR550##                    ##STR551##   O O                                        ##STR552##    180         ##STR553##                    ##STR554##   O O                                        ##STR555##    __________________________________________________________________________    181         ##STR556##                    ##STR557##   O O                                        ##STR558##    182         ##STR559##                    ##STR560##   O O                                        ##STR561##    183         ##STR562##                    ##STR563##   O O                                        ##STR564##    184         ##STR565##                    ##STR566##   O O                                        ##STR567##    185         ##STR568##                    ##STR569##   O O                                        ##STR570##    186         ##STR571##                    ##STR572##   O O                                        ##STR573##    187         ##STR574##                    ##STR575##   O O                                        ##STR576##    188         ##STR577##                    ##STR578##   O O                                        ##STR579##    189         ##STR580##                    ##STR581##   O O                                        ##STR582##    190         ##STR583##                    ##STR584##   O O                                        ##STR585##    191         ##STR586##                    ##STR587##   O O                                        ##STR588##    192         ##STR589##                    ##STR590##   O O                                        ##STR591##    193         ##STR592##                    ##STR593##   O O                                        ##STR594##    194         ##STR595##                    ##STR596##   O O                                        ##STR597##          n.sub.D.sup.20                                                            1.5659    195         ##STR598##                    ##STR599##   O O                                        ##STR600##          n.sub.D.sup.40                                                            1.5655    196         ##STR601##                    ##STR602##   O O                                        ##STR603##          n.sub.D.sup.20                                                            1.5684    197         ##STR604##                    ##STR605##   O O                                        ##STR606##          mp. 131-132.5.degr                                                            ee. C.    198         ##STR607##                    ##STR608##   O O                                        ##STR609##          n.sub.D.sup.20                                                            1.5625    199         ##STR610##                    ##STR611##   O O                                        ##STR612##          n.sub.D.sup.40                                                            1.5515    200         ##STR613##                    ##STR614##   O O                                        ##STR615##          n.sub.D.sup.20                                                            1.5500    201         ##STR616##                    ##STR617##   O O                                        ##STR618##    202         ##STR619##                    ##STR620##   O O                                        ##STR621##    203         ##STR622##                    ##STR623##   O O                                        ##STR624##          n.sub.D.sup.25                                                            1.5381    204         ##STR625##                    ##STR626##   O O                                        ##STR627##          n.sub.D.sup.20                                                            1.5528    205         ##STR628##                    ##STR629##   O O                                        ##STR630##          mp. 118-120.degree                                                            . C.    206         ##STR631##                    ##STR632##   O O                                        ##STR633##    207         ##STR634##                    ##STR635##   O O                                        ##STR636##    208         ##STR637##                    ##STR638##   O O                                        ##STR639##    209         ##STR640##                    ##STR641##   O O                                        ##STR642##    210         ##STR643##                    ##STR644##   O O                                        ##STR645##    211         ##STR646##                    ##STR647##   O O                                        ##STR648##    212         ##STR649##                    ##STR650##   O O                                        ##STR651##    213         ##STR652##                    ##STR653##   O O                                        ##STR654##          n.sub.D.sup.20                                                            1.5642    214         ##STR655##                    ##STR656##   O O                                        ##STR657##          mp. 125-127.degree                                                            . C.    215         ##STR658##                    ##STR659##   O O                                        ##STR660##    216         ##STR661##                    ##STR662##   O O                                        ##STR663##    217         ##STR664##                    ##STR665##   O O                                        ##STR666##          n.sub.D.sup.20                                                            1.5425    218         ##STR667##                    ##STR668##   O O                                        ##STR669##          mp. 124-125.degree                                                            . C.    219         ##STR670##                    ##STR671##   O O                                        ##STR672##    220         ##STR673##                    ##STR674##   O O                                        ##STR675##          n.sub.D.sup.50                                                            1.5520    221         ##STR676##                    ##STR677##   O O                                        ##STR678##    222         ##STR679##                    ##STR680##   O O                                        ##STR681##    223         ##STR682##                    ##STR683##   O O                                        ##STR684##    224         ##STR685##                    ##STR686##   O O                                        ##STR687##    225         ##STR688##                    ##STR689##   O O                                        ##STR690##    226         ##STR691##                    ##STR692##   O O                                        ##STR693##    227         ##STR694##                    ##STR695##   O O                                        ##STR696##    228         ##STR697##                    ##STR698##   S O   CH.sub.2 CH.sub.2    229         ##STR699##                    ##STR700##   S O   CH.sub.2CH.sub.2    230         ##STR701##                    ##STR702##   S O                                        ##STR703##    231         ##STR704##                    ##STR705##   S O                                        ##STR706##    232         ##STR707##                    ##STR708##   S O                                        ##STR709##    233         ##STR710##                    ##STR711##   S O                                        ##STR712##    234         ##STR713##                    ##STR714##   S                                    ##STR715##                                       CH.sub.2CH.sub.2    235         ##STR716##                    ##STR717##   S                                    ##STR718##                                       CH.sub.2CH.sub.2    236         ##STR719##                    ##STR720##   S                                    ##STR721##                                        ##STR722##    237         ##STR723##                    ##STR724##   O O                                        ##STR725##          n.sub.D.sup.20                                                            1.5480    238         ##STR726##                    ##STR727##   O O                                        ##STR728##          n.sub.D.sup.20                                                            1.5450    239         ##STR729##                    ##STR730##   O O                                        ##STR731##          mp.                                                            135- 136°                                                            C.    240         ##STR732##                    ##STR733##   O O                                        ##STR734##    241         ##STR735##                    ##STR736##   O O                                        ##STR737##    242         ##STR738##                    ##STR739##   O O                                        ##STR740##    243         ##STR741##                    ##STR742##   O O                                        ##STR743##    244         ##STR744##                    ##STR745##   S S                                        ##STR746##          oily    245         ##STR747##                    ##STR748##   S S                                        ##STR749##    246         ##STR750##                    ##STR751##   S S   CH.sub.2CH.sub.2    247         ##STR752##                    ##STR753##   S S   CH.sub.2CH.sub.2    248         ##STR754##                    ##STR755##   S S   CH.sub.2CH.sub.2    249         ##STR756##                    ##STR757##   S S                                        ##STR758##    250         ##STR759##                    ##STR760##   S S                                        ##STR761##    251         ##STR762##                    ##STR763##   S S                                        ##STR764##    252         ##STR765##                    ##STR766##   S S                                        ##STR767##    253         ##STR768##                    ##STR769##   S S                                        ##STR770##    254         ##STR771##                    ##STR772##   S S                                        ##STR773##    255         ##STR774##                    ##STR775##   S S                                        ##STR776##    256         ##STR777##                    ##STR778##   S S                                        ##STR779##    257         ##STR780##                    ##STR781##   S S                                        ##STR782##    258         ##STR783##                    ##STR784##   S S                                        ##STR785##    259         ##STR786##                    ##STR787##   S S                                        ##STR788##    260         ##STR789##                    ##STR790##   S S                                        ##STR791##    261         ##STR792##                    ##STR793##   S S                                        ##STR794##    262         ##STR795##                    ##STR796##   S S                                        ##STR797##    263         ##STR798##                    ##STR799##   S S                                        ##STR800##    264         ##STR801##                    ##STR802##   S S                                        ##STR803##    265         ##STR804##                    ##STR805##   S S                                        ##STR806##    266         ##STR807##                    ##STR808##   S S                                        ##STR809##    267         ##STR810##                    ##STR811##   S S                                        ##STR812##    268         ##STR813##                    ##STR814##   S S                                        ##STR815##    269         ##STR816##                    ##STR817##   S S                                        ##STR818##    270         ##STR819##                    ##STR820##   S S                                        ##STR821##    271         ##STR822##                    ##STR823##   S S                                        ##STR824##    272         ##STR825##                    ##STR826##   S S                                        ##STR827##    273         ##STR828##                    ##STR829##   S S                                        ##STR830##    274         ##STR831##                    ##STR832##   S S                                        ##STR833##    275         ##STR834##                    ##STR835##   S S                                        ##STR836##    276         ##STR837##                    ##STR838##   S S                                        ##STR839##    277         ##STR840##                    ##STR841##   S S                                        ##STR842##    278         ##STR843##                    ##STR844##   S S                                        ##STR845##    279         ##STR846##                    ##STR847##   S S                                        ##STR848##    280         ##STR849##                    ##STR850##   S S                                        ##STR851##    281         ##STR852##                    ##STR853##   S S                                        ##STR854##    282         ##STR855##                    ##STR856##   S S                                        ##STR857##    283         ##STR858##                    ##STR859##   S S                                        ##STR860##    284         ##STR861##                    ##STR862##   S S                                        ##STR863##    285         ##STR864##                    ##STR865##   S S                                        ##STR866##    286         ##STR867##                    ##STR868##   S S                                        ##STR869##    287         ##STR870##                    ##STR871##   S S                                        ##STR872##    288         ##STR873##                    ##STR874##   S S                                        ##STR875##    289         ##STR876##                    ##STR877##   S S                                        ##STR878##    290         ##STR879##                    ##STR880##   S S                                        ##STR881##    291         ##STR882##                    ##STR883##   S S   CH.sub.2 CH.sub.2 CH.sub.2    292         ##STR884##                    ##STR885##   S S   CH.sub.2 CH.sub.2 CH.sub.2    293         ##STR886##                    ##STR887##   S S                                        ##STR888##    294         ##STR889##                    ##STR890##   S S                                        ##STR891##    295         ##STR892##                    ##STR893##   S S                                        ##STR894##    296         ##STR895##                    ##STR896##   O O                                        ##STR897##    297         ##STR898##                    ##STR899##   O O                                        ##STR900##    298         ##STR901##                    ##STR902##   O O                                        ##STR903##    299         ##STR904##                    ##STR905##   O O                                        ##STR906##    300         ##STR907##                    ##STR908##   O O                                        ##STR909##    301         ##STR910##                    ##STR911##   O O                                        ##STR912##    302         ##STR913##                    ##STR914##   O O                                        ##STR915##    303         ##STR916##                    ##STR917##   O O                                        ##STR918##    304         ##STR919##                    ##STR920##   O O                                        ##STR921##    305         ##STR922##                    ##STR923##   O O                                        ##STR924##    306         ##STR925##                    ##STR926##   O O                                        ##STR927##    307         ##STR928##                    ##STR929##   O O                                        ##STR930##    308         ##STR931##                    ##STR932##   O O                                        ##STR933##    309         ##STR934##                    ##STR935##   O O                                        ##STR936##    310         ##STR937##                    ##STR938##   O O                                        ##STR939##    311         ##STR940##                    ##STR941##   O O                                        ##STR942##    312         ##STR943##                    ##STR944##   O O                                        ##STR945##    313         ##STR946##                    ##STR947##   O O                                        ##STR948##    314         ##STR949##                    ##STR950##   O O                                        ##STR951##    315         ##STR952##                    ##STR953##   O O                                        ##STR954##    316         ##STR955##                    ##STR956##   O O                                        ##STR957##    317         ##STR958##                    ##STR959##   O O                                        ##STR960##    318         ##STR961##                    ##STR962##   O O                                        ##STR963##    319         ##STR964##                    ##STR965##   O O                                        ##STR966##    320         ##STR967##                    ##STR968##   O O                                        ##STR969##    321         ##STR970##                    ##STR971##   O O                                        ##STR972##    322         ##STR973##                    ##STR974##   O O                                        ##STR975##    323         ##STR976##                    ##STR977##   O O                                        ##STR978##    324         ##STR979##                    ##STR980##   O O                                        ##STR981##    325         ##STR982##                    ##STR983##   O O                                        ##STR984##    326         ##STR985##                    ##STR986##   O O                                        ##STR987##    327         ##STR988##                    ##STR989##   O O                                        ##STR990##    328         ##STR991##                    ##STR992##   O O                                        ##STR993##    329         ##STR994##                    ##STR995##   O O                                        ##STR996##    330         ##STR997##                    ##STR998##   O O                                        ##STR999##    331         ##STR1000##                    ##STR1001##  O O                                        ##STR1002##    332         ##STR1003##                    ##STR1004##  O O                                        ##STR1005##    333         ##STR1006##                    ##STR1007##  O O                                        ##STR1008##    334         ##STR1009##                    ##STR1010##  O O                                        ##STR1011##    335         ##STR1012##                    ##STR1013##  O O                                        ##STR1014##    336         ##STR1015##                    ##STR1016##  O O                                        ##STR1017##    337         ##STR1018##                    ##STR1019##  O O                                        ##STR1020##    338         ##STR1021##                    ##STR1022##  O O                                        ##STR1023##    339         ##STR1024##                    ##STR1025##  O O                                        ##STR1026##    340         ##STR1027##                    ##STR1028##  O O                                        ##STR1029##    341         ##STR1030##                    ##STR1031##  S S                                        ##STR1032##         n.sub.D.sup.20                                                            1.6230    342         ##STR1033##                    ##STR1034##  O O   CH.sub.2 CH.sub.2 CH.sub.2                                                            mp. 70-73°                                                            C.    343         ##STR1035##                    ##STR1036##  O O                                        ##STR1037##         n.sub.D.sup.20                                                            1.5550    344         ##STR1038##                    ##STR1039##  O O                                        ##STR1040##         n.sub.D.sup.20                                                            1.5477    345         ##STR1041##                    ##STR1042##  O O                                        ##STR1043##         n.sub.D.sup.25                                                            1.5419    346         ##STR1044##                    ##STR1045##  O O                                        ##STR1046##         n.sub.D.sup.25                                                            1.5389    347         ##STR1047##                    ##STR1048##  O O                                        ##STR1049##         n.sub.D.sup.25                                                            1.5331    348         ##STR1050##                    ##STR1051##  O O                                        ##STR1052##         n.sub.D.sup.20                                                            1.5360    349         ##STR1053##                    ##STR1054##  O O                                        ##STR1055##         mp. 91-93°                                                            C.    350         ##STR1056##                    ##STR1057##  S S                                        ##STR1058##         n.sub.D.sup.20                                                            1.6064    351         ##STR1059##                    ##STR1060##  O O                                        ##STR1061##         n.sub.D.sup.20                                                            1.5330    352         ##STR1062##                    ##STR1063##  O O                                        ##STR1064##         n.sub.D.sup.20                                                            1.5228    353         ##STR1065##                    ##STR1066##  O O   CH.sub.2 CH.sub.2 CH.sub.2                                                            mp. 77-80°                                                            C.    354         ##STR1067##                    ##STR1068##  O O                                        ##STR1069##         n.sub.D.sup.20                                                            1.5627    355         ##STR1070##                    ##STR1071##  O O                                        ##STR1072##         n.sub.D.sup.20                                                            1.5436    356         ##STR1073##                    ##STR1074##  S S                                        ##STR1075##         n.sub.D.sup.20                                                            1.6421    357         ##STR1076##                    ##STR1077##  O O                                        ##STR1078##         n.sub.D.sup.50                                                            1.5824    358         ##STR1079##                    ##STR1080##  O O                                        ##STR1081##         n.sub.D.sup.50                                                            1.5600    359         ##STR1082##                    ##STR1083##  O O   CH.sub.2 CH.sub.2 CH.sub.2                                                            n.sub.D.sup.20                                                            1.5760    360         ##STR1084##                    ##STR1085##  O O                                        ##STR1086##         n.sub.D.sup.20                                                            1.5692    361         ##STR1087##                    ##STR1088##  O O                                        ##STR1089##         n.sub.D.sup.20                                                            1.5830    362         ##STR1090##                    ##STR1091##  S S   CH.sub.2 CH.sub.2    n.sub.D.sup.20                                                            1.6380    363         ##STR1092##                    ##STR1093##  S S   CH.sub.2 CH.sub.2    mp. 54-58°                                                            C.    364         ##STR1094##                    ##STR1095##  O O   CH.sub.2 CH.sub.2 CH.sub.2                                                            n.sub.D.sup.20                                                            1.5493    365         ##STR1096##                    ##STR1097##  O O                                        ##STR1098##         n.sub.D.sup.20                                                            1.5354    366         ##STR1099##                    ##STR1100##  O O                                        ##STR1101##         n.sub.D.sup.20                                                            1.5309    367         ##STR1102##                    ##STR1103##  O O                                        ##STR1104##         n.sub.D.sup.20                                                            1.5225    368         ##STR1105##                    ##STR1106##  O O                                        ##STR1107##         n.sub.D.sup.20                                                            1.5290    369         ##STR1108##                    ##STR1109##  O O                                        ##STR1110##    __________________________________________________________________________

EXAMPLE 6 Preparation of intermediate ##STR1111##

To a suspension of 17.8 g of nicotinyl chloride hydrochloride, 38.2 g ofdiphenyl and 100 ml of chlorobenzene, 33.3 g of aluminum chloride wasadded under ice-cooling and the resulting mixture was heated underreflux for six hours. After cooling, the reaction mixture was pouredinto a solution of ice/hydrochloric acid and washed with chloroform. Theaqueous layer was made alkaline with aqueous sodium hydroxide solutionand extracted with chloroform. The organic layer was washed with waterand dried over anhydrous sodium sulfate. After removal of the sodiumsulfate, the solvent was removed under reduced pressure to give 9.1 g of3-(4-phenylbenzoyl)-pyridine, mp. 112°-115° C.

EXAMPLE 7 Preparation of intermediate ##STR1112##

To 40 ml of a solution of 5.28 g of 6-chloronicotinoyl chloride inbenzene, 16 g of aluminum chloride was added under ice-cooling and theresulting mixture was heated under reflux for six hours. After cooling,the reaction mixture was poured into a solution of ice/hydrochloric acidand extracted with ether. The organic phase was washed with water anddried over anhydrous sodium sulfate. After filtering off the sodiumsulfate and distilling off the solvent, 4.6 g of3-benzoyl-6-chloropyridine was obtained. m.p.: 39°-40° C.

The following compounds can be prepared by the same method as describedabove: ##STR1113## BIOTEST EXAMPLES

Known comparison compounds employed: ##STR1114##

EXAMPLE 8 Activity test against Helminthosporium leaf spot (activecompounds were sprayed onto leaves and stalks)

Formulation of Active Compounds:

Compound to be tested: 30 parts

Organic solvent (xylene): 55 parts

Emulsifier:

Polyoxyethylenealkylphenyl ether: 8 parts

Calcium alkylbenzenesulfonate: 7 parts

The prescribed dosage of the emulsion obtained above is prepared bydilution with water.

Test Procedures:

Rice plants (Kusabue Variety) were grown in porcelain pots each having adiameter of 12 cm. The rice plants, at the 3-4 leaf stage, were sprayedwith the preparation of active compound in an amount of 50 ml per 3pots. On the next day, the plants were sprayed two times with asuspension of spores of the Gomahagarebyo-causing fungus which had beenartificially grown and kept in a moisture chamber at 25° C. and 100%relative humidity for 24 hours. After the artifical inoculation, theplants were placed in the greenhouse at 22°-30° C.

Seven days after the inoculation, the infection of the rice plants wasdetermined and recorded according to the following assessment scale:

    ______________________________________    Infection Rating   Infection Degree    ______________________________________    0                  non    1                  very slight    2                  slight    3                  medium    4                  great    5                  serious    ______________________________________

The percent protection was calculated employing the following equation:##EQU1## wherein A represents the average infection degree in thecontrol (untreated) pots: and

B represents the average infection degree in the treated pots.

The results of this test are given in Table 2.

                  TABLE 2    ______________________________________                 Active ingredient                               Protection    Compound No. concentration (ppm)                               (%)    ______________________________________     1           500           100     2           500           100     3           500           100    10           500           100    16           500           100    17           500           100    19           500           100    20           500           100    22           500           100    31           500           100    32           500           100    35           500           100    37           500           100    41           500           100    Comparison    E-1          500            47    E-2          500            60    E-3          500            43    ______________________________________

EXAMPLE 9: Controlling test for powdery mildew on cucumber

Test Procedure:

A test compound in the form of emulsion, which was prepared inaccordance with Example 8, was sprayed by using a spray gun on acucumber plant (variety: Tokiwajibai) at 2-leaf stage true leaf culturedin a porous pot 9 cm in diameter. One day after the spraying, thesuspension of spore of the pathogen (Sphaerotheca fuliginea) wasinoculated by spraying. After leaving in a thermostable chamber at 23°C., the degree of infection was determined based on the rate of lesionarea on the 10th day to calculate the controlling effect.

    ______________________________________    Infection degree                   Rate of lesion area (%)    ______________________________________    0              0    0.5            less than 2    1              3-5    2               6-15    3              16-30    4              31-50    5              more than 51     ##STR1115##    ______________________________________

The results of this test are given in Table 3.

                  TABLE 3    ______________________________________                 Active ingredient                               Protection    Compound No. concentration (ppm)                               (%)    ______________________________________     42          100           100     57          100           100     58          100           100     60          100           100     75          100           100    100          100           100    130          100           100    194          100           100    196          100           100    200          100           100    213          100           100    214          100           100    Comparison    E-1          100            20    ______________________________________

EXAMPLE 10 Herbicidal test/water surface treatment/weeds in locationswhere rice plants are grown under irrigation

Formulation of Active Compounds:

Carrier: 5 parts by weight of acetone

Emulsifier: 1 part by weight of benzyloxy polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amount of carrier and withthe stated amount of emulsifier, and the resulting emulsifiableconcentrate was then diluted with water to the desired concentration.

Test Procedure:

Each of several pots, each having a size of 25×20×9 cm and an area of1/2,000 are, was filled with soil taken from a paddy field.Rice-seedlings (Nihonbare Variety) of the 2.5-leaf stage, with anaverage height of 15 cm, were transplanted into these pots. Each pot hastwo zones each including one stock consisting of three plants. Then,seeds of the following weeds were sown in each of the pots, which waskept under wet conditions:

barnyard grass (Echinochloa);

flatsedge (Cyperus);

monochoria (Monochoria); and

annual broad-leaved weeds such as false pimpernel (Lindernia), toothcup(Rotala), waterstarwort (Elatine), red stem (Ammannia) and dopatrium(Dopatrium).

After 2 days, water was supplied into each of the pots up to 2-3 cm indepth.

Five days after the transplantation of the rice seedlings, the emulsionof the active compound, which had been prepared in the manner mentionedabove, was applied to each of the pots in a predetermined amount bymeans of a pipette. After that, the water sheet was kept in a thicknessof about 3 cm.

Four weeks after the application of the active compound, the degree ofdamage to the weeds and the degree of phytotoxicity on the rice plantswere determined, and recorded according to the following assessmentscale:

    ______________________________________                 Herbicidal effect of active    Rating       compound on weeds in %*    ______________________________________    5            95% or more (fatal effect)    4            at least 80% and less than 95%    3            at least 50% and less than 80%    2            at least 30% and less than 50%    1            at least 10% and less than 30%    0            less than 10% (no effect)    ______________________________________                 Phytotoxic effect of active    Rating       compound on crops in %*    ______________________________________    5            at least 90% (fatal phytotoxicity)    4            at least 50% and less than 90%    3            at least 30% and less than 50%    2            at least 10% and less than 30%    1            more than 0% and less than 10%    0            0% (no phytotoxicity)    ______________________________________     *These values (%) are those obtained by comparing the test data in the     treated plant section with the test data in the control (untreated) plant     section.

The test results are shown in Table 4.

                                      TABLE 4    __________________________________________________________________________           Amount                 Herbicidal effect on weeds           of        Spikerush,   Annual           active                 Barn-                     Slender      broad-                                      Phytotoxic    Active compound                 yard                     (Eleo-                           Flat-                              Mono-                                  leaved                                      effect on    compound           (kg/ha)                 grass                     charis)                           sedge                              choria                                  weeds                                      rice plants    __________________________________________________________________________     1     2     3   5     4  5   5   0     2     2     5   5     5  5   5   0    12     2     4   5     5  5   5   0    19     2     5   5     5  5   5   0    32     2     5   5     5  5   5   0    Comparison    E-2    2     0   0     0  0   0   0    E-3    2     0   0     0  0   0   0    __________________________________________________________________________

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A 3-substituted pyridine of the formula##STR1116## wherein A represents sulfur,B represents sulfur, R¹represents hydrogen, halogen, lower alkyl or halo-lower alkyl, R²represents hydrogen, halogen, lower alkyl phenyl, halo-lower alkyl orphenoxy, l is 0 or 1, m is an integer from 1 to 4, n is an integer from1 to 5, R³ and R⁴ each represent hydrogen, hydroxy-lower alkyl loweralkoxy-lower alkyl, lower alkyl, benzyloxy-lower alkyl, halo-lower alkylor carboxy-lower alkyl, or R³ and R⁴ form a hydrocarbon ring having 6 or12 carbon atoms in total together with the carbon atoms to which theyare bonded.
 2. A compound according to claim 1, wherein such compound is2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane of the formula ##STR1117##
 3. Acompound according to claim 1, wherein such compound is4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane of the formula##STR1118##
 4. A compound according to claim 1, wherein such compound is2-(4-fluorophenyl)-4-methyl-2-(3-pyridyl)-1,3-dithiolane ##STR1119## 5.A compound according to claim 1, wherein such compound is2-(2,4-difluorophenyl)-4-methyl-2-(3-pyridyl)-1,3-dithiolane ##STR1120##6. A fungicidal or herbicidal composition comprising a fungicidally orherbicidally effective amount of a compound according to claim 1 and adiluent.
 7. A method of combating fungi which comprises applying to suchfungi or to a fungus habitat a fungicidally effective amount of acompound according to claim
 1. 8. The method according to claim 7,wherein such compound is2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane,4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane,2-(4-fluorophenyl)-4-methyl-2-(3-pyridyl)-1,3-dithiolane or2-(2,4-difluorophenyl)-4-methyl-2-(3-pyridyl)-1,3-dithiolane.
 9. Amethod of combating unwanted vegetation which comprises applying to suchvegetation or to a locus from which is desired to exclude suchvegetation a herbicidally effective amount of a compound according toclaim
 1. 10. The method according to claim 9, wherein such compoundis2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane,4-methyl-2-phenyl-2-(pyridin-3-yl)-1,3-dithiolane,2-(4-fluorophenyl)-4-methyl-2-(3-pyridyl)-1,3-dithiolane or2-(2,4-difluorophenyl)-4-methyl-2-(3-pyridyl)-1,3-dithiolane.